HYDROPHOBIC DISPERSING COPOLYMER

Abstract

The invention provides an aqueous particle-dispersing composition of an organic pigment comprising a copolymer prepared by radical polymerization of a carboxylic monomer, a styrenic monomer, and a hydrophobic polyalkoxylated ester or a hydrophobic polyalkoxylated amide. The invention also relates to this copolymer and its use as a particle dispersant for organic pigments, particularly in a coating composition.

Description

Title of the invention: COPOLYMER HYDROPHOBIC DISPERSANT

[0001] The invention provides an aqueous particle dispersing composition of an organic pigment comprising a copolymer prepared by radical polymerization of a carboxylic monomer, a styrenic monomer, and a hydrophobic polyalkoxylated ester or a hydrophobic polyalkoxylated amide. The invention also relates to this copolymer and its use as a dispersant for organic particles, particularly in a coating composition.

[0002] Many technical fields use organic materials in the form of particles which are generally suspended in aqueous compositions, for example for their transport, storage or use in coating compositions, in particular in paint or coating compositions, or even in textile printing compositions.

[0003] The particle size must be controlled, as well as the various rheological components of these suspensions, particularly for high concentrations of organic matter. These different properties are difficult to control, especially since these organic materials possess different particle size distributions, morphological characteristics, or rheological properties.

[0004] Methods for preparing aqueous compositions of organic matter, particularly pigments or organic fillers, are known. In particular, methods are known that employ additives during the various stages of preparation of these compositions, notably additives to control their rheology or particle size. It is important to have methods for preparing aqueous compositions of organic matter that are stable not only shortly after preparation but also several hours or days later. Viscosity drift phenomena must be controlled because these phenomena can lead to gelation of the prepared suspensions, making their handling difficult or even impossible. Similarly, particle sedimentation phenomena must be avoided or significantly slowed down.In addition to stability control, viscosity control of aqueous suspensions of organic matter particles is also essential.

[0005] It is also important to be able to prepare aqueous suspensions of organic matter particles with a high dry extract. A high dry extract of these aqueous suspensions of organic matter particles allows, in particular to increase the productivity of methods that use these suspensions and to limit the costs and resources for their transport.

[0006] There is therefore a need for rheology control agents for aqueous compositions of organic particles. The invention provides a solution to all or part of the problems of rheological control agents in the prior art. Thus, the invention provides an aqueous composition A comprising at least one copolymer P obtained by a polymerization reaction, in an aqueous medium and in the presence of at least one initiating compound T: (a) of at least one anionic compound (a) comprising at least one polymerizable olefinic unsaturation and at least one carboxylic acid function or one of its salts, (b) of at least one non-ionic hydrocarbon compound (b) arylvinyl, (c) of at least one compound (c) of formula I: [Chem I] r! in which: - R1 independently represents H or CH3. - R2 independently represents H or a hydrophobic hydrocarbon group, - L1 independently represents a group chosen from C(O)O, C(O)N(H) and ch2o, - L2 independently represents a group chosen from (CH2CH2O)X, (CH2 CH(CH3)O)y, (CH(CH3)CH2O)z and their combinations and - x, y and z, identical or different, independently represent 0 or an integer or decimal number between 1 and 150 and the sum x+y+z is between 2 and 150.

[0007] Preferably for composition A according to the invention, compound (a) is selected from acrylic acid, methacrylic acid, a salt of acrylic acid, a salt of methacrylic acid, an oligomer of acrylic acid, an oligomer of methacrylic acid, a salt of an acrylic acid oligomer, a salt of a methacrylic acid oligomer, and combinations thereof. Methacrylic acid, a salt of methacrylic acid, an oligomer of methacrylic acid, a salt of a methacrylic acid oligomer, and combinations thereof are the preferred compounds (a). Methacrylic acid is the most preferred.

[0008] Preferably for composition A according to the invention, compound (b) is selected from styrene, alpha-methylstyrene, p-methylstyrene, o-vinyltoluene, p- vinyltoluene, p-acetoxystyrene, p-bromostyrene, p- / e / 7-butylstyrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, dopamine-methacrylamide, dopamine-acrylamide, allyl-catechol and their combinations. Styrene is the preferred compound (b).

[0009] Preferably for composition A according to the invention, compound (c) is a compound of formula I in which: - R1 represents CH3; or - R2 represents H or a CH3 group or a hydrophobic hydrocarbon group comprising from 4 to 40 carbon atoms; preferably, a linear, branched or cyclic hydrocarbon group, saturated, unsaturated or aromatic; more preferably, a linear, branched or cyclic hydrocarbon group, saturated, unsaturated or aromatic comprising from 4 to 40 carbon atoms; or - L2 independently represents a (CH2-CH2O)X group or a combination of (CH2-CH2O)X, (CH2CH(CH3)O)y and (CH(CH3)CH2O)Z groups; or - x, y and z, identical or different, independently represent 0 or an integer or decimal number between 1 and 140 and the sum x+y+z is between 2 and 140.

[0010] More preferably for composition A according to the invention, compound (c) is a compound of formula I in which: - R1 represents CH3, - R2 represents H or a CH3 group or a hydrophobic hydrocarbon group comprising from 4 to 40 carbon atoms; preferably, a linear, branched or cyclic hydrocarbon group, saturated, unsaturated or aromatic; more preferably, a linear, branched or cyclic hydrocarbon group, saturated, unsaturated or aromatic comprising from 4 to 40 carbon atoms, - L2 independently represents a (CH2-CH2O)X group or a combination of (CH2-CH2O)X, (CH2CH(CH3)O)y and (CH(CH3)CH2O)Z groups and - x independently represents an integer or decimal number between 2 and 140, - y and z represent 0 or: - x represents an integer or decimal number between 2 and 40 and - the sum y+z is between 2 and 20.

[0011] More preferably for composition C according to the invention, compound (c) is a compound of formula I in which R1 represents CH3.

[0012] Also more preferably according to the invention, R2 represents H or a CH3 group or a linear or branched Cg-Cα-alkyl group or a C6-Cβ-aryl group; much more preferably, a linear or branched C8-Cγ2-alkyl group or a C6-Cβ-aryl group; even more preferably, a linear C8-Cγ2-alkyl group or a linear C8-Cβ4-alkyl group or a C6-C 4 o-aryl, for example a styryl group, a cardanyl group, a tri(styryl)phenyl group.

[0013] Much more preferably, R2 represents H, CH3, a branched Ci6-alkyl group from a Guerbet alcohol or a tri(styryl)phenyl group.

[0014] Essentially, according to the invention, composition A comprises a copolymer P prepared by polymerizing compounds (a), (b), and (c), alone or combined with one or more other monomers. Advantageously, according to the invention, the polymerization reaction may also involve at least one other compound selected from: - another anionic compound (d) different from compound (a), preferably a compound (d) chosen from itaconic acid, maleic acid, maleic anhydride and their combinations; - a sulfur compound (e), preferably a compound (e) selected from 2-acrylamido-2-methylpropane sulfonic acid, a salt of 2-acrylamido-2-methylpropane sulfonic acid, 2-(methacryloyloxy)ethanesulfonic acid, a salt of 2-(methacryloyloxy)ethanesulfonic acid, sodium methallyl sulfonate, sodium vinyl sulfonate, styrene sulfonate and their combinations, preferably styrene sulfonate; - a non-ionic compound (f) comprising at least one polymerizable olefinic unsaturation and different from compound (b), preferably at least one polymerizable ethylenic unsaturation, and in particular a non-ionic compound (f) comprising a polymerizable vinyl function, more preferably a non-ionic compound (f) selected from vinylcaprolactam, esters of an acid comprising at least one monocarboxylic acid function, in particular an ester of an acid selected from acrylic acid, methacrylic acid and their combinations, for example hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, alkyl acrylate, in particular C-Cio-alkyl acrylate or C5-Cio-alkyl acrylate, C-Cio-alkyl methacrylate or C5-Cio-alkyl methacrylate, for example methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, acrylate isobutyl, n-butyl acrylate, alkyl methacrylate, methyl methacrylate,ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, isobutyl methacrylate, n-butyl methacrylate, aryl acrylate; preferably in an amount of less than 5% by weight, also preferably from 0.01% by weight to 4% by weight, in particular from 0.02% by weight to 4% by weight or from 0.02% by weight to 2% by weight, in particular from 0.02% by weight to 1% by weight, of compound (f) relative to the total amount by weight of monomers; , - a crosslinking compound (g) or a compound (g) comprising at least two olefinic unsaturations; preferably in an amount of less than 5% by weight, also of preference of 0.01% by weight to 4% by weight, in particular of 0.02% by weight to 4% by weight or of 0.02% by weight to 2% by weight, in particular of 0.02% by weight to 1% by weight, of compound (g) relative to the total amount by weight of monomers.

[0015] Preferably according to the invention, the polymerization reaction does not involve a non-ionic compound (f) selected from Ci-C4-alkyl acrylate and Ci-C4-alkyl methacrylate, in particular methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, isobutyl acrylate, n-butyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, isobutyl methacrylate, n-butyl methacrylate. Preferably according to the invention, the non-ionic compound (f) is selected from vinylcaprolactam, hydroxyethylacrylate, hydroxypropylacrylate, hydroxyethylmethacrylate, hydroxypropylmethacrylate, C5-Ci0-alkyl acrylate, preferably C5-C8-alkyl acrylate, C5-Ci0-alkyl methacrylate, preferably C5-C8-alkyl methacrylate, aryl acrylate, phenyl acrylate, benzyl acrylate, phenoxyethyl acrylate, aryl methacrylate, phenyl methacrylate, benzyl methacrylate, phenoxyethyl methacrylate.

[0016] Preferably according to the invention, the copolymer P is prepared in the absence of a crosslinking compound and in the absence of a compound comprising at least two olefinic unsaturations.

[0017] Also preferably according to the invention, the polymerization reaction can also utilize styrene sulfonate.

[0018] The copolymer P according to the invention is prepared by a radical polymerization reaction carried out in the presence of an initiator compound T. Preferably according to the invention, the initiator compound T is chosen from peroxides, hydroperoxides, persulfates, azo compounds and their respective combinations or associations with an ion chosen from Fe11, Fe111, Cu1, Cu11. Preferably, the initiating compound T is selected from hydrogen peroxide, tert-butyl hydroperoxide, benzoyl peroxide, acetyl peroxide, lauryl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, ammonium persulfate, an alkali metal persulfate and in particular sodium persulfate, potassium persulfate, 4,4'-azobis-4-cyanopentanoic acid (ACPA), 4,4'-azobis(4-cyanovaleric acid) (CAS No. 2638-94-0), 2,2'-azobis(2-methylpropionamidine) dihydrochloride (CAS No. 2997-92-4), azo-bis-isobutyronitrile (AZDN or AIBN) and their combinations.Preferably, compound T is chosen from sodium persulfate and hydrogen peroxide associated with an Fe11 ion.

[0019] Preferably according to the invention, the polymerization reaction is carried out in water, alone or combined with at least one polar, protic solvent, preferably an alcohol, preferably isopropanol. More preferably the polymerization reaction is carried out in water alone.

[0020] According to the invention, the polymerization reaction can, in addition, be carried out in the presence of at least one chain transfer agent; preferably a chain transfer agent used in a concentration ranging from 0.1% by weight to 10% by weight, preferably from 0.5% by weight to 8% by weight or from 1% by weight to 6% by weight, relative to the amount by weight of monomers.

[0021] Also preferably the chain transfer agent can be chosen from primary thiols, mercaptans and their combinations, preferably chosen from n-dodecyl mercaptan, tert-dodecyl mercaptan, tert-nonyl mercaptan, thiolactic acid, mercaptopropionic acid, mercaptoethanol, thioglycolic acid, l,8-dhnercapto-3,6-dioxaoctane (DMDO - CAS No.14970-87-7), a compound comprising P1, a compound comprising P111, a compound comprising SIV; preferably a chain transfer agent selected from a mercaptan, a compound comprising phosphite, a compound comprising hypophosphite, a compound comprising hydrogen sulfite; more preferably a chain transfer agent selected from n-dodecyl mercaptan, phosphorous acid, sodium phosphite, hypophosphorous acid, sodium hypophosphite, sodium hydrogen sulfite; much more preferably a chain transfer agent selected from sodium hypophosphite and sodium hydrogen sulfite. .

[0022] According to the invention, the polymerization reaction generally leads to an aqueous dispersion of polymer P. Preferably, according to the invention, polymer P is obtained in the form of particles. More preferably, the polymer P particles have an average size, measured using a particle size analyzer, of less than 500 nm, preferably less than 300 nm. Also preferably, the polymer P particles have an average size ranging from 10 nm to 500 nm or from 10 nm to 300 nm.

[0023] The invention also relates to the preparation of the aqueous composition A according to the invention. Thus, the invention provides a method for preparing an aqueous composition A according to the invention comprising the polymerization reaction in an aqueous medium and in the presence of at least one initiating compound T, preferably carried out at a temperature below 100°C, more preferably at a temperature ranging from 20°C to 95°C: (a) of at least one anionic compound (a) comprising at least one polymerizable olefinic unsaturation and at least one carboxylic acid function or one of its salts, (b) of at least one non-ionic hydrocarbon compound (b) arylvinyl, (c) of at least one compound (c) of formula I: [Chem I] 'CR' in which: - R1 independently represents H or CH3. - R2 independently represents H or a hydrophobic hydrocarbon group, - L1 independently represents a grouping chosen from C(O)O, C(O)N(H) and ch2o, - L2 independently represents a group chosen from (CH2CH2O)X, (CH2 CH(CH3)O)y, (CH(CH3)CH2O)z and their combinations and - x, y and z, whether identical or different, independently represent 0 or an integer or decimal number between 1 and 150, and the sum x+y+z is between 2 and 150.

[0024] Essentially, composition A according to the invention comprises at least one copolymer P. The invention also relates to a copolymer P according to the invention or obtained by a polymerization reaction in aqueous medium and in the presence of at least one initiating compound T, preferably carried out at a temperature below 100°C, more preferably at a temperature ranging from 20°C to 95°C, : (a) of at least one anionic compound (a) comprising at least one polymerizable olefinic unsaturation and at least one carboxylic acid function or one of its salts, (b) of at least one non-ionic hydrocarbon compound (b) arylvinyl, (c) of at least one compound (c) of formula I: [Chem I] in which: - R1 independently represents H or CH3. - R2 independently represents H or a hydrophobic hydrocarbon group, - L1 independently represents a grouping chosen from C(O)O, C(O)N(H) and ch2o, - L2 independently represents a group chosen from (CH2CH2O)X, (CH2 CH(CH3)O)y, (CH(CH3)CH2O)z and their combinations and - x, y and z, identical or different, independently represent 0 or an integer or decimal number between 1 and 150 and the sum x+y+z is between 2 and 150.

[0025] The copolymer P possesses particularly interesting properties, notably dispersing properties of organic pigment particles, which are very useful in many technical fields. Thus, the invention provides an aqueous composition C comprising at least one aqueous composition A according to the invention or at least one copolymer P according to the invention and particles of at least one organic pigment Q, preferably an organic pigment Q selected from carbon particles, carbon black, acetylene black, Ketjen black, carbon fibers, carbon nanotubes, carbon nanofibers, graphene, tempered carbon, graphite carbon fibers, graphite carbon particles, organic coloring pigment, organic textile printing dye, printing ink, for example a white coloring pigment, a yellow coloring pigment, an orange coloring pigment, a red coloring pigment, a blue coloring pigment, a green coloring pigment, and a black coloring pigment.

[0026] The invention also relates to the preparation of the aqueous composition C according to the invention. Thus, the invention provides a method for preparing an aqueous composition C according to the invention comprising mixing in water at least one composition A or at least one copolymer P according to the invention and particles of at least one organic pigment Q.

[0027] Preferably according to the invention, the organic pigment Q is selected from carbon particles, carbon black, acetylene black, Ketjen black, carbon fibers, carbon nanotubes, carbon nanofiber, graphene, tempered carbon, graphite carbon fibers, graphite carbon particles, organic coloring pigment, organic textile printing dye, printing ink, for example a white coloring pigment, a yellow coloring pigment, an orange coloring pigment, a red coloring pigment, a blue coloring pigment, a green coloring pigment and a black coloring pigment.

[0028] Within the aqueous composition C according to the invention, the proportions of the different ingredients may vary. Preferably, the aqueous composition C according to the invention comprises: - from 0.05% by dry weight to 5% by dry weight of copolymer P, - from 95% by dry weight to 99.95% by dry weight of organic pigment Q, compared to the quantities by dry weight of ingredients P and Q.

[0029] Advantageously, the use of the copolymer P in the aqueous composition C according to the invention allows for effective control of its viscosity; in particular, its Brookfield viscosity measured at 25°C and 100 rpm for a relative quantity by dry weight of polymer P compared to the quantity by dry weight of pigment Q, which is less than 45%, preferably less than 40% or less than 35%. Thus, Preferably, the aqueous composition C according to the invention has a Brookfield viscosity measured at 25°C and 100 rpm which is less than 1200 mPa.s, preferably less than 1000 mPa.s, for a relative quantity by dry weight of polymer P compared to the quantity by dry weight of pigment Q, which is less than 45%, preferably less than 40%, more preferably less than 35%.

[0030] The copolymer P thus allows the preparation of various compositions comprising organic pigments and optionally other substances, including a substance for binding the organic pigment particles to a substrate. Thus, the invention provides a coating composition R comprising the copolymer P or an aqueous composition A according to the invention in combination with organic pigment particles Q and at least one binding compound L. Preferably, the coating composition R according to the invention is selected from: - a coating composition RI comprising at least one binder compound L and at least one composition C according to the invention, - a coating composition R2 comprising at least one binder compound L, particles of at least one organic pigment Q according to the invention and at least one copolymer P according to the invention, - a coating composition R3 comprising at least one binder compound L, particles of at least one organic pigment Q according to the invention and at least one aqueous composition A according to the invention.

[0031] Preferably according to the invention, the binder L is selected from a natural binding agent such as starch, carboxymethyl cellulose (CMC), hydroxyethyl celluloses, casein, proteins, alginates, or a synthetic binding agent such as latex. More preferably, the binder L can be selected from a styrene-butadiene polymer, a styrene-acrylic polymer, a styrene-acetate polymer, a vinyl acetate polymer, a vinyl acetate homopolymer, a vinyl acetate copolymer, a vinyl versatate homopolymer, a vinyl versatate copolymer, and combinations thereof. In particular, the binder L can be selected from: - a vinyl acetate homopolymer; - a copolymer comprising at least vinyl acetate and ethylene, a vinyl acetate and acrylate copolymer, a vinyl acetate and methacrylate copolymer, a vinyl acetate, ethylene and acrylate copolymer, a vinyl acetate, ethylene and methacrylate copolymer, a vinyl acetate, acrylate and methacrylate copolymer; - a vinyl versatate homopolymer; - a copolymer of vinyl versatate and ethylene, a copolymer of vinyl versatate and acrylate, a copolymer of vinyl versatate and methacrylate, a copolymer of vinyl versatate, ethylene and acrylate, a copolymer of vinyl, ethylene and methacrylate versatate, a copolymer of vinyl, acrylate and methacrylate versatate; - a copolymer of vinyl acetate and vinyl versatate, a copolymer of vinyl acetate, vinyl versatate and ethylene, a copolymer of vinyl acetate, vinyl versatate and acrylate, a copolymer of vinyl acetate, vinyl versatate and methacrylate, a copolymer of vinyl acetate, vinyl versatate, ethylene and acrylate, a copolymer of vinyl acetate, vinyl versatate, ethylene and methacrylate, a copolymer of vinyl acetate, vinyl versatate, ethylene, acrylate and methacrylate and - their combinations.

[0032] Within the composition R according to the invention, the proportions of the different ingredients may vary. Preferably, the composition R according to the invention comprises: - from 0.2% by dry weight to 6% by dry weight of copolymer P, - from 60% by dry weight to 90% by dry weight of organic pigment Q, - from 2% by dry weight to 20% by dry weight of binding agent L, compared to the quantities by dry weight of ingredients P, Q and L.

[0033] The RI, R2 and R3 coating compositions according to the invention can be prepared by mixing, in particular by mixing in water and preferably under agitation, their different ingredients, the binding agent L and the organic pigment particles Q, and where applicable of composition A or of the copolymer P according to the invention or of composition C.

[0034] The invention also provides a method for dispersing particles of at least one organic pigment Q, preferably an organic pigment Q selected from carbon particles, carbon black, acetylene black, Ketjen black, carbon fibers, carbon nanotubes, carbon nanofiber, graphene, tempered carbon, graphite carbon fibers, graphite carbon particles, organic coloring pigment, organic textile printing dye, printing ink, for example a white coloring pigment, a yellow coloring pigment, an orange coloring pigment, a red coloring pigment, a blue coloring pigment, a green coloring pigment and a black coloring pigment.

[0035] Preferably according to the invention, the method of dispersing organic pigment particles Q comprises mixing the pigment Q under agitation with at least one composition A according to the invention or with at least one copolymer P according to the invention.

[0036] The advantageous, particular or preferred characteristics of composition A according to the invention define methods for preparing this composition, copolymers P, compositions C as well as coating compositions R and dispersion methods according to the invention which are also advantageous, particular or preferred.

[0037] The various aspects of the invention can be illustrated by examples.

[0038] Preparation and characterization of PI to P5 polymers according to the invention

[0039] In a 2 L reactor, 261 g of water and 15 g of 29% sodium lauryl sulfate in water are introduced and heated to a temperature of 85°C. In a beaker, 4.9 g of 29% sodium lauryl sulfate in water, 137 g of water, 73 g of methacrylic acid, 71 g of styrene, 15 g of dodecyl mercaptan and 28 g of compound Ml (compound c of formula I in which R1 represents CH3, R2 represents H, L1 represents a C(O)O group, L2 represents a combination of (CH2CH2O), (CH2CH(CH3)O) and (CH(CH3)CH2O) groups, y+z represents 10 and x represents approximately 30). 0.6 g of initiator compound (ammonium persulfate) and 0.06 g of sodium bisulfite are introduced into the reactor, and the reagent mixture is added over 2 hours while maintaining the temperature at 85°C. Heating is continued for 1 hour. The medium is neutralized with 99 g of 50% potassium hydroxide in water to obtain a pH of 10 and diluted with 179 g of water to obtain a 25% dry extract.

[0040] Similarly, polymers P2 to P5 are prepared by replacing compound M1 respectively with the following compounds: - M2: compound c of formula I in which R1 represents CH3, R2 represents CH3, L1 represents a C(O)O group, L2 represents a (CH2CH2O)X group and x represents 120, - M3: compound c of formula I in which R1 represents CH3, R2 represents a branched Ci6-alkyl group from a Guerbet alcohol, L1 represents a C(O)O group, L2 represents a (CH2CH2O)X group and x represents 25, - M4: compound c of formula I in which R1 represents CH3, R2 represents CH3, L1 represents a C(O)N(H) group, L2 represents a combination of (CH2CH2O), (CH2CH(CH3)O) and (CH(CH3)CH2O) groups, y+z represents 10 and x represents 30, - M5: compound c of formula I in which R1 represents CH3, R2 represents a tristyrylphenyl group, L1 represents a C(O)O group, L2 represents a (CH2CH2O)X group and x represents 25.

[0041] The viscosity at 100 rpm of the PI polymers at P5 is then measured at 25°C using a Brookfield viscometer equipped with a spindle 5. The polymer particle sizes are measured using a Zetasizer Malvern instrument. The characteristics of the PI polymers at P5 are presented in Table 1.

[0042] [tab 1] Polymer PI P2 P3 P4 PS Viscosity (mPa.s.) 300 340 1100 230 1300 Particle size (nm) 140 230 120 160 90

[0043] Preparation and characterization of aqueous compositions of organic pigment A1 to A5 according to the invention

[0044] In a beaker, and with stirring, an aqueous composition is prepared having a dry extract of 40% by weight and comprising beta-modified Cu-phthalocyanine blue organic pigment (“Orion” Monolite Blue 515303 (PB 15:3) - CAS No. 147-14-8) and the polymer PI, which is introduced in an amount sufficient to obtain a Brookfield viscosity, measured at 25°C and 100 rpm using a viscometer equipped with a spindle 5, that is less than 500 mPa·s. The composition Al comprises 100 parts by weight of water, 70 parts by weight of pigment, 1.8 parts by weight of an antifoaming agent (“BYK” 024), and the polymer PL

[0045] Similarly, compositions A2 to A5 are prepared by replacing polymer PI respectively with polymers P2 to P5 according to the invention.

[0046] The relative quantities by dry weight of polymer in relation to the quantity by dry weight of pigment and the results of the viscosity measurements are presented in Table 2.

[0047] [tab 2] Composition Al A2 A3 A4 A5 Polymer Quantity (%) 15 15 15 15 15 Viscosity (mPa.s) 120 200 175 110 150

[0048] Preparation and characterization of aqueous carbon black compositions A6 to A10 according to the invention

[0049] In a beaker, and with stirring, an aqueous composition is prepared having a dry extract of 40% by weight and comprising carbon black (“Orion” Special 4 black) and the polymer PI, which is introduced in an amount sufficient to obtain a Brookfield viscosity, measured at 25°C and 50 rpm using a viscometer equipped with a spindle 5, that is less than 1000 mPa·s. Composition A6 comprises 60 parts by weight of water, 25 parts by weight of pigment, 1 part by weight of an antifoaming agent (“BYK” 024), and the polymer PL

[0050] Similarly, compositions A7 and A10 are prepared by replacing polymer PI respectively with polymers P2 to P5 according to the invention.

[0051] The relative quantities by dry weight of polymer in relation to the quantity by dry weight of carbon black and the results of the viscosity measurements are presented in Table 3.

[0052] [tab 3] Composition A 6 A7 A8 A9 AI0 Polymer Quantity (%) 35 35 35 35 35 Viscosity (mPa.s) 150 900 800 600 500

[0053] The P polymers according to the invention allow for the efficient dispersion of different types of organic pigments. The quantities of P polymer used are particularly small.

Claims

Demands

1. Aqueous composition A comprising at least one copolymer P obtained by a polymerization reaction, in aqueous medium and in the presence of at least one initiator compound T, of: (a) at least one anionic compound (a) comprising at least one polymerizable olefinic unsaturation and at least one carboxylic acid function or one of its salts, (b) at least one nonionic hydrocarbon compound (b) arylvinyl, (c) at least one compound (c) of formula I: [Chem I] R' A . '1 / R" in which: - R1 independently represents H or CH3. - R2 independently represents H or a hydrophobic hydrocarbon group, - L1 independently represents a group chosen from C(O)O, C(O)N(H) and CH2O, - L2 independently represents a group chosen from (CH2 CH2O)x, (CH2CH(CH3)O)y, (CH(CH3)CH2O)z and their combinations and - x, y and z, identical or different, independently represent 0 or an integer or decimal number between 1 and 150 and the sum x +y+z is between 2 and 150.

2. Aqueous composition A according to claim 1 wherein compound (a) is selected from acrylic acid, methacrylic acid, a salt of acrylic acid, a salt of methacrylic acid, an oligomer of acrylic acid, an oligomer of methacrylic acid, a salt of an acrylic acid oligomer, a salt of a methacrylic acid oligomer and combinations thereof; preferably selected from methacrylic acid, a salt of methacrylic acid, an oligomer of methacrylic acid, a salt of a methacrylic acid oligomer and combinations thereof; more preferably methacrylic acid.

3. Aqueous composition A according to any one of claims 1 or 2 wherein compound (b) is selected from styrene, alpha-methylstyrene, p-methylstyrene, o-vinyltoluene, p-vinyltoluene, p-acetoxystyrene, p-bromostyrene, p-tert-butylstyrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, dopamine-methacrylamide, dopamine-acrylamide, allyl-catechol and combinations thereof.

4. Aqueous composition A according to any one of claims 1 to 3 wherein compound (c) is a compound of formula I in which: - R1 represents CH3; or - R2 represents H or a CH3 group or a hydrophobic hydrocarbon group comprising from 4 to 40 carbon atoms; preferably, a linear, branched or cyclic hydrocarbon group, saturated, unsaturated or aromatic; more preferably, a linear, branched or cyclic hydrocarbon group, saturated, unsaturated or aromatic comprising from 4 to 40 carbon atoms; more preferably, a linear or branched C6-C40-alkyl group or a C6-C4o-aryl group; much more preferably, a linear or branched C8-C32-alkyl group or a C6-C40-aryl group;even more preferably, a linear C8-C32-alkyl group or a linear C8-C24-alkyl group or a C6-C4 O-aryl group, for example a styryl group, a cardanyl group, a tri(styryl)phenyl group; or - L2 independently represents a (CH2-CH2O)X group or a combination of (CH2-CH2O)X, (CH2CH(CH3)O)y and (CH(CH3)CH2O)z groups; or - x, y and z, identical or different, independently represent 0 or an integer or decimal number between 1 and 140 and the sum x + y + z is between 2 and 140.;

5. Aqueous composition A according to any one of claims 1 to 4, wherein the polymerization reaction also involves at least one other compound selected from: - another anionic compound (d) different from compound (a), preferably a compound (d) selected from itaconic acid, maleic acid, maleic anhydride and combinations thereof; - a sulfur compound (e), preferably a compound (e) selected from 2-acrylamido-2-methylpropanesulfonic acid, a salt of 2-acrylamido-2-methylpropanesulfonic acid, the acid 2-(methacryloyloxy)ethanesulfonic acid, a salt of 2-(methacryloyloxy)ethanesulfonic acid, sodium methallyl sulfonate, sodium vinyl sulfonate, styrene sulfonate and their combinations, preferably styrene sulfonate; - a non-ionic compound (f) comprising at least one polymerizable olefinic unsaturation and different from compound (b), preferably at least one polymerizable ethylenic unsaturation, and in particular a non-ionic compound (f) comprising a polymerizable vinyl function, more preferably a non-ionic compound (f) selected from vinylcaprolactam, esters of an acid comprising at least one monocarboxylic acid function, in particular an ester of an acid selected from acrylic acid, methacrylic acid and their combinations, for example hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, alkyl acrylate, in particular C-Cio-alkyl acrylate or C5-CiO-alkyl acrylate, C-Cio-alkyl methacrylate or C5-CiO-alkyl methacrylate, for example methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, acrylate isobutyl, n-butyl acrylate, alkyl methacrylate, methyl methacrylate,ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, isobutyl methacrylate, n-butyl methacrylate, aryl acrylate; preferably vinylcaprolactam, hydroxyethylacrylate, hydroxypropylacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, C5-C10-alkyl acrylate, preferably C5-C8-alkyl acrylate, C5-C10-alkyl methacrylate, preferably C5-C8-alkyl methacrylate, aryl acrylate, phenyl acrylate, benzyl acrylate, phenoxyethyl acrylate, aryl methacrylate, phenyl methacrylate, benzyl methacrylate, phenoxyethyl methacrylate; preferably in an amount of less than 5% by weight, also preferably from 0.01% by weight to 4% by weight, in particular from 0.02% by weight to 4% by weight or from 0.02% by weight to 2% by weight, in particular from 0.02% by weight to 1% by weight, of compound (f) relative to the total amount by weight of monomers; - a crosslinking compound (g) or a compound (g) comprising at least two olefinic unsaturations; preferably in an amount of

6. less than 5% by weight, also preferably from 0.01% by weight to 4% by weight, in particular from 0.02% by weight to 4% by weight or from 0.02% by weight to 2% by weight, in particular from 0.02% by weight to 1% by weight, of compound (g) relative to the total amount by weight of monomers. Aqueous composition A according to any one of claims 1 to 5, wherein: - the initiating compound T is selected from peroxides, hydroperoxides, persulfates, azo compounds and their respective combinations or associations with an ion selected from Fe11, Fe111, Cu1, Cu11, preferably an initiating compound T selected from hydrogen peroxide, tert-butyl hydroperoxide, benzoyl peroxide, acetyl peroxide, lauryl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, ammonium persulfate, an alkali metal persulfate and in particular sodium persulfate, potassium persulfate, 4,4'-azobis-4-cyanopentanoic acid (ACPA), 4,4'-azobis(4-cyanovaleric acid) (CAS No. 2638-94-0), 2,2'-azobis(2-methylpropionamidine) dihydrochloride (CAS No. 2997-92-4), azo-bisisobutyronitrile (AZDN or AIBN) and their combinations; or - the polymerization reaction is carried out in water, alone or combined with at least one polar, protic solvent, preferably an alcohol, more preferably isopropanol; preferably the polymerization reaction is carried out in water alone; or - the polymerization reaction is, moreover, carried out in the presence of at least one chain transfer agent; preferably a chain transfer agent used in a concentration ranging from 0.1% by weight to 10% by weight, preferably from 0.5% by weight to 8% by weight or from 1% by weight to 6% by weight, relative to the amount by weight of monomers; also preferably a chain transfer agent selected from primary thiols, mercaptans and their combinations, preferably selected from n-dodecyl mercaptan, tert-dodecyl mercaptan, tert-nonyl mercaptan, thiolactic acid, mercaptopropionic acid, mercaptoethanol, thioglycolic acid, 1,8-dhnercapto-3,6-dioxaoctane (DMDO - CAS No. 14970-87-7), a compound comprising P1, a compound comprising P11, a compound comprising SIV; preferably a transfer agent chain selected from a mercaptan, a compound comprising phosphite, a compound comprising hypophosphite, a compound comprising hydrogen sulfite; more preferably a chain transfer agent selected from n-dodecyl mercaptan, phosphorous acid, sodium phosphite, hypophosphorous acid, sodium hypophosphite, sodium hydrogen sulfite.

7. Method of preparing an aqueous composition A according to any one of claims 1 to 6 comprising the polymerization reaction in aqueous medium and in the presence of at least one initiating compound T, preferably carried out at a temperature below 100°C, more preferably at a temperature from 20°C to 95°C, of: (a) at least one anionic compound (a) comprising at least one polymerizable olefinic unsaturation and at least one carboxylic acid function or one of its salts, (b) at least one nonionic hydrocarbon compound (b) arylvinyl, (c) at least one compound (c) of formula I: [Chem I] R' X.- ''FT in which: - R1 independently represents H or CH3, - R2 independently represents H or a hydrophobic hydrocarbon group, - L1 independently represents a group chosen from C(O)O, C(O)N(H) and CH2O, - L2 independently represents a group chosen from (CH2 CH2O)x, (CH2CH(CH3)O)y, (CH(CH3)CH2O)z and their combinations and - x, y and z, identical or different, independently represent 0 or an integer or decimal number between 1 and 150 and the sum x +y+z is between 2 and 150.

8. Copolymer P defined according to any one of claims 1 to 7 or obtained by a polymerization reaction in aqueous medium and in the presence of at least one initiating compound T, preferably carried out at a temperature below 100°C, more preferably at a temperature ranging from 20°C to 95°C, of: (a) at least one anionic compound (a) comprising at least one polymerizable olefinic unsaturation and at least one carboxylic acid function or one of its salts, (b) at least one nonionic hydrocarbon compound (b) arylvinyl, (c) at least one compound (c) of formula I: [Chem I] R ''L4' ''R* in which: - R1 independently represents H or CH3, - R2 independently represents H or a hydrophobic hydrocarbon group, - L1 independently represents a group selected from C(O)O, C(O)N(H) and CH2O, - L2 independently represents a group selected from (CH2 CH2O)x, (CH2CH(CH3)O)y, (CH(CH3)CH2O)z and their combinations and - x, y and z, identical or different, independently represent 0 or an integer or decimal number between 1 and 150 and the sum x + y + z is between 2 and 150.

9. 9. Aqueous composition C comprising at least one aqueous composition A according to any one of claims 1 to 6 or at least one copolymer P according to claim 8 and particles of at least one organic pigment Q, preferably an organic pigment Q selected from carbon particles, carbon black, acetylene black, Ketjen black, carbon fibers, carbon nanotubes, carbon nanofiber, graphene, tempered carbon, graphite carbon fibers, graphite carbon particles, organic coloring pigment, organic textile printing dye, printing ink, for example a white coloring pigment, a yellow coloring pigment, an orange coloring pigment, a red coloring pigment, a blue coloring pigment, a green coloring pigment and a black coloring pigment.

10. 10. Method of preparing an aqueous composition C according to claim 9 comprising mixing in water of at least one composition A or at least one copolymer P, defined according to any one of claims 1 to 8, and particles of at least one organic pigment Q, preferably an organic pigment Q selected from carbon particles, carbon black, acetylene black, Ketjen black, carbon fibers, carbon nanotubes, carbon nanofiber, graphene, tempered carbon, graphite carbon fibers, graphite carbon particles, organic coloring pigment, organic textile printing dye, printing ink, for example a white coloring pigment, a yellow coloring pigment, an orange coloring pigment, a red coloring pigment, a blue coloring pigment, a green coloring pigment and a black coloring pigment.

11. 11. Coating composition R selected from: - a coating composition RI comprising at least one binder compound L and at least one composition C according to claim 9, - a coating composition R2 comprising at least one binder compound L, particles of at least one organic pigment Q according to claim 10 and at least one copolymer P according to claim 8, - a coating composition R3 comprising at least one binder compound L, particles of at least one organic pigment Q according to claim 10 and at least one aqueous composition A according to any one of claims 1 to 6.

12. 12. Method for dispersing particles of at least one organic pigment Q, preferably an organic pigment Q selected from carbon particles, carbon black, acetylene black, Ketjen black, carbon fibers, carbon nanotubes, carbon nanofiber, graphene, tempered carbon, graphite carbon fibers, graphite carbon particles, organic coloring pigment, organic textile printing dye, printing ink, for example a white coloring pigment, a yellow coloring pigment, an orange coloring pigment, a red coloring pigment, a blue coloring pigment, a green coloring pigment and a black coloring pigment; preferably comprising mixing the pigment Q under stirring with at least one composition A according to any one of claims 1 to 6 or with at least one copolymer P according to claim 8.